Carl ludwig muller



Urvrrno 'Srn'rns ATENT retest CARL LUDW'IG MULLER, OF LUDVIGSHAFEN,GERMANY, ASSIGNOR TO THE BADISCHE ANILIN AND SODA FABRIK, OF SAME PLACE.

BROWN-YELLOW DYE.

SPECIFICATION forming part of Letters Patent No. 5l6,17-7, datedSeptember 10, 1895.

Application filed April 11, 1395. $erial No. 545,383 (Specimens) To allwhom it may concern: phenyZ-awramin and its conversion into new I Be itknown that], CARL LUDWIG MULLER, -c0Z0ring-matzfer.-Mix together aboutforty doctor of philosophy,asubject of the King of (40) parts oftetramethyl-diamido-beuzo- Bavaria, residing atLugwigshafen'on-thephenone, twen ty-seven (27) parts of meta- Rhine, inthe Kingdom of Bavaria and Emphenylene-diamin-dihydrochlorate and aboutpire of Germany, have invented new and usenine (9) parts ofmeta-phenylene-diamin-base 55 fullmproveinents in the Manufacture of newand heat the mixture on the oil-bath in a Basic Coloring-Matter, ofwhich the following closed enameled vessel provided with an outis aspecification. let for the vapors evolved, and furnished with to Myinvention consists in the manufacture a stirrer. Stir continuously andmaintain of new basic coloring-matter which appears the temperatureof'the oil-bath at about from 63 in its chemical constitution to berelated to one hundred and ninety-five to two hundred the acridin seriesand to resemble phosphin and fifteen degrees centigrade (195 to 215C.)in its properties. The said new coloring The substituted auramin dye isfirst formed,

matter is obtained from certain substituted but it is graduallyconverted into new color auramins by treatment, as hereinafterdeing-mat-ter. Withdraw test portions from 6 scribed. The substitutedauramins, which time to time, dissolve them in dilute hydroappear to bemost suited for conversion into chloric acid, and boil the solution. Thesubthe new coloring-matters, are the meta-amidostitutcd auramin yieldsunder these condi- 2 phenyl-auramins and ineto-amido-tolyl-aurationsanorange-yellowsolutiomwhich becomes mine, which can be regarded asderivatives nearly colorless on boiling, while the new col- 7c ofmeta-phenylene and toluylene-diamin on oring-rnatter yields abrownish-yellow soluthe one hand and on the other hand of tetration,which remains unchanged on boiling. methyl ortetra-ethyl-diamido-diphenyl-me- Interrupt the heating'of the whole meltwhen theme. The hydrochlorates of the said subthe tests show that nofurther change into stituted auramius on heating either by themthe newc0l0ring-n1atter is taking place. 75 selves or admixed withmeta-phenylenedia- This usually takes about from four to seven min andmeta-toluylene-diaminas such or t to 7) hours. Allow the melt to cool.It as hydrochlorates-with or without the addisolidifies to adark-colored mass possessing a tion of a condensing agent yield the newcolgreenish metallic luster, dissolve the wholein oring-matter. As aninstance of a suitable about four hundred (400) parts of boiling 8ocondensing agent,I mention chloride of zinc. water, to which abouttwenty (20') parts of The substituted auramins can be preparedhydrochloric acid (containing about thirty in the manner described inthe specification per cent. (30%) real acid HCl) have been of EnglishLetters Patent No. 5,741, of 1884, added. Allow the liquid to cool andthen or any other known or suitable method for filterand precipitate thecoloringmatter from 8 the preparation of auramiu dyes may be used. thefiltered solution by the addition of com- I have foundthat it is usuallynot necessary mon salt and chlorid of zinc. Collectthe preto use pureisolated substituted auramins, cipitate and mix it with twenty (20)parts of but that the crude melt or reaction product hydrochloric acid(containing about thirty containing the said substituted auramins canper cent. (30%) real acid HCl) and heat the be and preferably isdirectly used in the promixture on the water-bath in order to obtaincess according to this invention. a readily soluble salt. Next evaporateto dry- The following example will serve to further ness and reduce topowder.

5 illustrate the nature of 'the invention, but it Under certainconditions a brownish colorcan be varied in many respects, and I do noting-matter is formed besides the desired col- 9 5 confine myself to thesaid example. The oring-matter. This can readily be removed parts are byweight. from the product by taking advantage of its Example: Productionof a meta-amide lesser solubility in hydrochloric acid. The

formation of this product has especially'been i noticedwhen thetemperature of the melt has the methyl derivative.

visableto add zinc chlorid to the melt. The

risen too high, it it it I it 7 it Instead of meta-phenylene-diamin inthe above example meta-toluylene-dianiin can be used, and similarly alsothe tetra-ethyl diamido-benzo-phenone can be used instead of In thiscase'it is adcoloring-inatter resulting when making these variationsispractically thesame.

The same coloring-matter can-also be ob-i.

tained by heating the hydrols' derived from themethane compoundshereinbefore men'- matter, however obtained,ischaracterized by tionedwith the meta-diamins,togetherwith the hydrochlorates thereof. My newcoloringthe following properties: it occurs as a dark brownish powder,it is readily soluble in water and spiritsof wine, giving abrownishyellow solution possessing a green fluorescence. It ispractically insoluble in benzene and ether. ltismoreparticularly.c-haractee ized and distinguished from knowncoloringmatters which most'nearly resemble it by its behavior withconcentrated hydrochloricacid in which it dissolves, giving anorange-brown solution-possessinga yellowish fluorescence. It can also bedistingushed, as a rule, by t-reating an aqueous solution with nitrousacid.

Thus on adding hy-drochlorieacid and sodiu m nitrite the solution turnsdark greenish or gets discolored and on staudinga brown precipitate isformed. t i

My new coloring-matter dyes cotton mor- --additioi1 of common salt andchloride dented: with tannin with brownish-yellow shades, and it is alsosuitable for producing usefulbrownish-yellow shades onleather. Now, whatI claim is- 7 1. The process for the manufacture of basic coloringmatter which consists in heating the hydrochlorate of asubstitutedauramine such as meta-amido-phenyl-auramine, then allowing the melt tocool, then dissolving the same I in water acidulated' with hydrochloricacid, then precipitating the coloring matter'by the substantially asdescribed.

2. As a new article of manufacture the new basic coloring matter whichcan be obtained 0 by heating the hydrochlorate of a substituted auramineand which occurs as a dark brownish powderreadily soluble in water-andin spirits of wine giving brownish yellow solutions pos- I sessingagreen fluorescence, soluble inconcentrated-hydrochloricacidyiel'dinganorange brown solution possessinga yellowish 'tluorescence, and which on treatment with nitrous acid inaqueous solution yields a dark green so I ish or discolored solutionfrom which a brown precipitate separates substantially as described.

In testimony whereof I have hereunto set :my hand in the presence of twosubscribing witnesses. CARL LUDWIG MULLER.

Witnesses:

ERNEST F. EHRHART, 7 PAUL JULIUs.

of zinc

